Flavoring with a hydroxy cyclohexenone derivative

ABSTRACT

Processes and compositions are described for the use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma, tobacco flavor and aroma, perfume and perfumed article aroma augmenting, enhancing and imparting compositions and as foodstuff, chewing gum, toothpaste, medicinal product, tobacco, perfume and perfumed article aroma imparting materials of hydroxy cyclohexenone derivatives having the generic formula: ##STR1## wherein one of X and Y is a keto moiety having the structure: ##STR2## and the other of X and Y is a carbinol moiety having the structure: ##STR3## and wherein R is C 1  -C 5  alkyl.

BACKGROUND OF THE INVENTION

The present invention relates to hydroxy cyclohexenone derivativeshaving the generic formula: ##STR4## wherein one of X and Y is a ketomoiety having the structure: ##STR5## and the other of X and Y is acarbinol moiety having the structure: ##STR6## and wherein R is C₁ -C₅alkyl produced by the processes of our invention and novel compositionsusing one or more of such hydroxy cyclohexenone derivatives to augmentor enhance the flavor and/or aroma of consumable materials or impartflavor and/or aroma to consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply and to provide more uniform properties in the finishedproduct.

Citrus/labdanum, sweet and woody aromas with sweet, woody, earthy andlabdanum flavor characteristics are particularly desirable for many usesin foodstuff flavorings, chewing gum flavors, toothpaste flavors andmedicinal product flavors.

Green, minty, herbaceous, strong fruity aromas with earthy, mossy notesare desirable in several types of perfume compositions, perfumedarticles and colognes.

Sweet, tobacco-like, floral and green aromas prior to smoking and brighttobacco-like notes on smoking are particularly desirable in tobaccos andtobacco flavoring materials.

The compound having the structure: ##STR7## is disclosed by Maheshwari,et al in Canadian Journal of Chemistry, Vol. 48, 1970, pages 3265-3268;however, the organoleptic uses of such compound are not set forth.

A compound having the common name "Blumenol-C" having the structure:##STR8## is disclosed as having been isolated from Burley tobacco flavorby Demole and Enggist at page 2088, Helv.Chim.Acta., Vol. 57, Fasc. 7(1974) and also by Aasen, et al, Acta.Chem.Scandinavia, B 28 (1974),pages 285-8.

Also disclosed are U.S. Pat. Nos. 3,793,375 and 3,839,421 as beinguseful as plant growth regulators are compounds having the structures:##STR9##

However, none of the compounds of the prior art have been heretoforedetermined to have the organoleptic properties that the compounds of theinstant invention have.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the NMR spectrum for one of the compounds producedaccording to Example II, namely,4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one and2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one.

FIG. 2 represents the Infrared spectrum for one of the compoundsproduced according to Example II, namely,4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one and2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one.

FIG. 3 represents the NMR spectrum for one of the compounds producedaccording to Example II,4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one.

FIG. 4 represents the Infrared spectrum for one of the compoundsproduced according to Example II,4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one.

FIG. 5 represents the NMR spectrum for the compound prepared accordingto Example IV, 4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one.

FIG. 6 represents the Infrared spectrum for the compound preparedaccording to Example IV,4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product, toothpaste and tobacco compositions andflavoring compositions therefor having citrus/labdanum, sweet and woodyaromas with sweet, woody, earthy and labdanum flavor characteristics;novel perfume compositions, colognes and perfumed articles having green,minty, herbaceous, strong fruity aromas with earthy and mossy notes; andtobaccos and tobacco flavoring compositions having sweet, tobacco-like,floral and green aromas prior to smoking and bright tobacco-like noteson smoking, may be provided by the utilization of one or more hydroxycyclohexenone derivatives having the formula: ##STR10## wherein one of Xand Y is a keto moiety having the structure: ##STR11## and the other ofX and Y is a carbinol moiety having the structure: ##STR12## infoodstuffs, chewing gums, toothpastes, medicinal product flavors,perfumes, perfumed articles, colognes, tobaccos and tobacco flavors.

The hydroxy cyclohexenone derivatives useful as indicated supra, may beproduced by one or two processes:

(i) subjecting 1,3,5,5-tetramethylcyclohexa-1,3-diene to an oxidationstep comprising continuously insufflating air or oxygen through saiddiene at a temperature of between 15° and 30° C, while agitating saiddiene and irradiating said diene with ultraviolet light in the presenceof an alkali metal hydroxide and Rose Bengal according to the followingreaction sequence: ##STR13##

(ii) reacting 2,7,9,9-tetramethyl-1,4-dioxaspiro[4,5]dec-6-en-8-one withan alkyl lithium to form a lithium salt and then hydrolyzing the saltwhile simultaneously deketalizing the resulting compound according tothe following reaction sequence: ##STR14## wherein R₁ is C₁ -C₄ alkyland R₂ is lower alkyl or H.

The photo-oxidation reaction is preferably carried out in an inertsolvent such as methanol or a methanol-benzene mixture in the presenceof a reaction sensitizer such as Rose Bengal and a base such as sodiumhydroxide and potassium hydroxide. The photo-oxidation is carried out bybubbling oxygen through the reaction mass and the time of reaction aswell as the rate of reaction is a function of the following variables:

1. Bubble size of oxygen;

2. Throughput of oxygen per unit of time;

3. Pressure;

4. Concentration of base in reaction mass; and

5. Concentration of UV sensitizer in reaction mass.

Higher pressures give rise to longer oxygen residence time therebypermitting shorter times of reaction and greater yields per unit time.Higher concentrations of reaction sensitizer give rise to fasterreaction rates:up to sensitizer concentrations of 0.5 gm per liter andsensitizer:diene ratios 0.5:4, whereat increase in sensitizerconcentration does not give rise to any material increase in reactionrate. It is preferable to carry out the photo-oxidation reaction at atemperature of between 15° and 30° C with room temperature being mostconvenient.

In the reaction of alkyl lithium with the compound having the structure:##STR15## any ketal may be used in addition to the cyclic ketalsexemplified above; e.g., diethyl ketals, dimethyl ketals and ethyleneglycol ketals, wherein R₂ is H; or R₂ could be alkyl (C₁ -C₈).

The first step of the reaction is preferably carried out in the presenceof an inert solvent such as n-hexane or cyclohexane at a temperature ofbetween 15° C and the reflux temperature of the solvent; preferably atroom temperature. The alkyl lithium in inert solution is preferablyadded dropwise to a solution of the ketal reactant until no additionalexotherm occurs.

The hydrolysis of the lithium salt moiety and the ketal moiety thentakes place merely with addition of water. The temperature of the secondreaction may vary from 15° C up to 70° C, but most conveniently andpreferably may take place at room temperature.

The compound having the structure: ##STR16## is a novel compound havingunexpected, unobvious properties over the known compound of the genus ofour invention having the structure: ##STR17##

Examples and organoleptic properties of materials produced according tothe aforementioned processes are as follows:

                                      TABLE I                                     __________________________________________________________________________                       ORGANOLEPTIC PROPERTIES                                                                             TOBACCO AROMA                        NAME       STRUCTURE                                                                             FLAVOR     FRAGRANCE  AND FLAVOR                           __________________________________________________________________________    2-hydroxy-2,4,6,6- tetramethylcyclo- hex-2-en-1-one                                       ##STR18##                                                                            Citrus/labdanum, sweet woody aroma characteristics                            with sweet, woody, earthy, labdanum/ citrus flavor                            characteristics at 10 ppm.                                                               Minty, green, herb- aceous                                                               Sweet tobacco-like. floral,                                                   green aroma with slight cooling                                               effect prior to smoking and                                                   bright tobacco-like aroma and                                                 taste with sweet and floral                                                   nuances in the main- stream and                                               in the sidestream.                   4-butyl-4-hydroxy- 3,5,5-trimethyl-2- cyclohexen-2-one                                    ##STR19##                                                                            Bitter chemical.                                                                         Strong fruity and earthy mossy aroma with                                     herbaceous, green, sweet, woody, minty and                                    slightly earthy nuances.                                                                 Sweet, hay-like, Virginia                                                     tobacco, flue-cured-like, aroma                                               with floral and sweet hay                                                     nuances prior to and on smoking                                               in the main and                      __________________________________________________________________________                                             side- streams.                   

When the hydroxy cyclohexenone derivatives of our invention are used asfood flavor adjuvants, the nature of the co-ingredients included witheach of the said hydroxy cyclohexenone derivatives in formulating theproduct composition will also serve to alter, modify, augment or enhancethe organoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the hydroxy cyclohexenone derivatives of our invention, andin addition, sweetening agents which may be sugars, including sucrose ordextrose and/or artifical sweeteners such as cyclamates or saccharin.Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehicles broadlycomprising stabilizers, thickeners, surface active agents, conditioners,other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like; buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal,beta, beta-dimethylacrolein, methyl-n-amyl ketone, n-hexanal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, -2-methyl-2-hepten-6-one,2-octanone, 2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methylfurfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten:1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethylnaphthalene, dodecane, methyldiphenyl,methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, 1-phellandrene, p-cymene, 1-alphapinene; pyrazines suchas 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the hydroxy cyclohexenonederivatives of our invention by not covering or spoiling theorganoleptic properties (aroma and/or taste) thereof; (ii) benon-reactive with the hydroxy cyclohexenone derivatives of our inventionand (ii) be capable of providing an environment in which the hydroxycyclohexenone derivatives can be dispersed or admixed to provide ahomogeneous medium. In addition, selection of one or more flavoringadjuvants, as well as the quantities thereof will depend upon theprecise organoleptic character desired in the finished product. Thus, inthe case of flavoring compositions, ingredient selection will vary inaccordance with the foodstuff, chewing gum, medicinal product,toothpaste or tobacco to which the flavor and/or aroma are to beimparted, modified, altered or enhanced. In contradistinction, in thepreparation of solid products, e.g., simulated foodstuffs, ingredientscapable of providing normally solid compositions should be selected suchas various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of thehydroxy cyclohexenone derivatives employed in a particular instance canvary over a relatively wide range, depending upon the desiredorganoleptic effects to be achieved. Thus, correspondingly, greateramounts would be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for purposes of enhancing thecomposition merely deficient in natural flavor or aroma. The primaryrequirement is that the amount selected be effective, i.e., sufficientto alter, modify or enhance the organoleptic characteristics of theparent composition, whether foodstuff per se, chewing gum per se,medicinal product per se, toothpaste per se, tobacco per se, orflavoring composition.

The use of insufficient quantities of the hydroxy cyclohexenonederivatives will, of course, substantially vitiate any possibility ofobtaining the desired results while excess quantities prove needlesslycostly and in extreme cases, may disrupt the flavor-aroma balance, thusproving self-defeating. Accordingly, the terminology "effective amount"and "sufficient amount" is to be accorded a significance in the contextof the present invention consistent with the obtention of desiredflavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions, toothpaste compositionsand tobacco compositions, it is found that quantities of the hydroxycyclohexenone derivatives ranging from a small but effective amount,e.g., 0.5 parts per million up to about 100 parts per million based ontotal composition are suitable. Concentrations in excess of the maximumquantity stated are not normally recommended, since they fail to provecommensurate enhancement of organoleptic properties. In those instances,wherein hydroxy cyclohexenone derivatives are added to the foodstuff asan integral component of a flavoring composition, it is, of course,essential that the total quantity of flavoring composition employed besufficient to yield an effective concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the hydroxy cyclohexenone derivatives inconcentrations from about 0.1% up to about 15% by weight based on thetotal weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the hydroxy cyclohexenone derivativeswith, for example, gum arabic, gum tragacanth, carrageenan and the like,and thereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form,e.g., a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and the hydroxycyclohexenone derivatives in a dry blender until the requisite degree ofuniformity is achieved.

It is presently preferred to combine with the hydroxy cyclohexenonederivatives of our invention, the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl anthranilate;

5-Methylfurfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

Damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-one);

Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene);

Beta-cyclohomocitral (2,2,6-trimethylcyclohex1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl)-norbornadiene prepared according to ExampleII of U.S. Pat. No. 3,911,028, issued on Oct. 7. 1975.

The hydroxy cyclohexenone derivatives of our invention and one or moreauxiliary perfume ingredients, including, for example, alcohols,aldehydes, nitriles, esters, cyclic esters and natural essential oils,may be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance, particularly and preferably inherbal fragrances. Such perfume compositions usually contain (a) themain note or the "bouquet" or foundation stone of the composition; (b)modifiers which round off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or morehydroxy cyclohexenone derivatives can be used to alter, modify orenhance the aroma characteristics of a perfume composition, for example,by utilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of hydroxy cyclohexenone derivatives of our invention whichwill be effective in perfume compositions as well as in perfumedarticles and colognes depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% of ahydroxy cyclohexenone derivative(s) or even less (e.g., 0.005% can beused to impart a green, minty, herbaceous, strong fruity aroma withearthy and mossy notes to soaps, cosmetics or other products. The amountemployed can range up to 70% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

The hydroxy cyclohexenone derivatives of our invention are useful [takenalong or together with other ingredients in perfume compositions] as anolfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such aslacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as creams, deodorants, hand lotions and sun screens; powders, suchas talcs, dusting powders, face powders and the like. When used as (an)olfactory component(s) as little as 1% of hydroxy cyclohexenonederivatives will suffice to impart an intense green note to herbalformulations. Generally, no more than 3% of hydroxy cyclohexenonederivatives based on the ultimate end product, is required in theperfume composition.

In addition, the perfume compositions or fragrance composition of ourinvention can contain a vehicle, or carrier for the hydroxycyclohexenone derivatives. The vehicle can be a liquid such as analcohol, a non-toxic alcohol, a non-toxic glycol, or the like. Thecarrier can also be an absorbent solid, such as a gum (e.g., gum arabic)or components for encapsulating the composition (such as gelatin).

It will thus be apparent that the hydroxy cyclohexenone derivatives ofour invention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrances(s) of a wide variety of consumable materials.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor includingmethods of making the same which overcome problems heretoforeencountered in the creation or enhancement of specific desired sweet,hay-like, Virginia tobacco-like, flue cured-like aromas with floral andsweet hay nuances. These notes, both prior to and on smoking in the mainstream and sidestream may now be readily controlled and maintained atthe desired uniform level regardless of variations in the tobaccocomponents of the blend; or the nature of the filter used in conjunctionwith the tobacco article.

This invention further provides improved tobacco additives and additivesfor materials used in the fabrication of tobacco articles and methodswhereby desirable sweet, hay-like, Virginia tobacco-like, fluecured-like aromas with floral and sweet hay nuances may be imparted tosmoking tobacco products and may be readily varied and controlled toproduce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient, one ormore of the hydroxy cyclohexenone derivatives of our invention.

In addition to the hydroxy cyclohexenone derivatives of our invention,other flavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with oneor more of the hydroxy cyclohexenone derivatives:

I. Synthetic Materials

Beta-methyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1,2-methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2,1-b)-furan;

4-Hydroxy hexanoic acid, gamma lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil;

Origanum oil.

An aroma and flavoring concentrate containing one or more of the hydroxycyclohexenone derivatives of our invention and, if desired, one or moreof the above indicated additional flavoring additives may be added tothe smoking tobacco material, to the filter or to the leaf or paperwrapper or to a filter which is part of the smoking article. The smokingtobacco material may be shredded, cured, cased and blended tobaccomaterial or reconstituted tobacco material or tobacco substitutes (e.g.,lettuce leaves) or mixtures thereof. The proportions of flavoringadditives may be varied in accordance with taste but insofar asenhancement or the imparting of sweet, hay-like, Virginia tobacco-like,flue cured-like aromas with floral and sweet hay nuances, we have foundthat satisfactory results are obtained if the proportion by weight ofthe sum total of the hydroxy cyclohexenone derivatives to smokingtobacco material is between 50 ppm and 500 ppm (.005%-.05%) of theactive ingredients to the smoking tobacco material. We have furtherfound that satisfactory results are obtained if the proportion by weightof the sum total of the hydroxy cyclohexenone derivatives used toflavoring material is between 0.05:1 and 0.50:1.

Any convenient method for incorporating the hydroxy cyclohexenonederivatives in the tobacco product may be employed. Thus, the hydroxycyclohexenone derivatives taken alone or along with other flavoringadditives may be dissolved in a suitable solvent such as ethanol,pentane, diethyl ether and/or other volatile organic solvents and theresulting solution may either be sprayed on the cured, cased and blendedtobacco material or the tobacco material or filter may be dipped intosuch solution. Under certain circumstances, a solution of hydroxycyclohexenone derivatives taken alone or taken further together withother flavoring additives as set forth above, may be applied by means ofa suitable applicator such as a brush or roller on the paper or leafwrapper for the smoking product, or it may be applied to the filter byeither spraying, or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have one or more hydroxycyclohexenone derivatives of our our invention in excess of the amountsor concentrations above indicated so that when blended with othertobaccos, the final product will have the percentage within theindicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of 4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one of ourinvention, in an amount to provide a tobacco composition containing 800ppm by weight of 4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one ona dry basis. Thereafter, the alcohol is removed by evaporation and thetobacco is manufactured into cigarettes by the usual techniques. Thecigarette when treated as indicated has a desired and pleasing sweet,hay-like, Virginia flue cured tobacco-like aroma with floral andmoss-like nuances detectable in the main and side streams when thecigarette is smoked.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco, and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. As stated supra, the hydroxy cyclohexenone derivatives ofour invention can be incorporated with materials such as filter tipmaterials, seam paste, packaging materials and the like which are usedalong with the tobacco to form a product adapted for smoking.Furthermore, the hydroxy cyclohexenone derivatives of our invention canbe added to certain tobacco substitutes of natural or synthetic origin(e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" asused throughout this specification is meant any composition intended forhuman consumption, by smoking or otherwise, whether composed of tobaccoplant parts or substitute materials or both.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims. All parts and percentages are by weight unlessotherwise indicated.

EXAMPLE I PREPARATION OF 1,3,5,5-TETRAMETHYLCYCLOHEXA-1,3-DIENE##STR20##

To a 5 liter flask fitted with a stirrer, thermometer, dropping funnel,reflux condenser, drying tube and nitrogen purge is charged 2100 ml (6.3moles) of a 3 m solution of methyl magnesium chloride intetrahydrofuran. The flask and contents are cooled to 0° C and 730 g(5.3 moles) of isophorone is added at 0°-5° C over a two hour period.The mixture is allowed to warm to room temperature and to standovernight. The reaction mixture is poured over a mixture of 2800 g ofice and 370 g of glacial acetic acid. When all the ice melts, the layersare separated and the organics are washed twice with 500 ml of water.The solvent is removed on a rotary evaporator and the product istransferred to a 2 liter flask fitted with a condenser and a waterseparator. Benzene (300 ml) and p-toluenesulfonic acid (0.5 g) are addedand the mixture is refluxed until no additional water separated. Theproduct is distilled on a 12 inch Goodloe column using a reflux ratio of9:1. A total of 494 g of product is obtained (b.p. 66°-67° C at 42 mmHg) which is predominantly 1,3,5,5,-tetramethylcyclohexa-1,3-diene.

EXAMPLE II PREPARATION OF4-HYDROXY-2,4,6,6-TETRAMETHYLCYCLOHEX-2-EN-1-ONE AND2,4,4,6-TETRAMETHYLCYCLOHEXA-2,5-DIENE-1-ONE ##STR21##

A solution of 40 g (0.3 moles) of 1,3,5,5-tetramethylcyclohexa-1,3-diene(prepared as in Example I), 13 g (0.23 moles) of potassium hydroxide and0.3 g of Rose Bengal in 600 ml of methanol is placed in a flask andirradiated with a 450 watt tungsten photo lamp over a period of twohours. A steady stream of oxygen is bubbled through the solution duringirradiation. At the end of the two hour irradiation period analysis of asample of the reaction mixture by GLC (10 feet × 1/8 inch 10% Carbowax20M on Chromasorb W, programmed from 80°-220° C at 8°/min.) shows thatthe starting material is completely consumed and two products hadformed. Both products are trapped from the GLC column and analyzed. Thefirst (about 20% of the reaction product) is found to be2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one (compound A) and exhibitsthe following spectral properties:

    ______________________________________                                        NMR (δ) ppm                                                                              Interpretation                                               ______________________________________                                        1.2              (s, 6H)                                                      1.9              (s, 6H)                                                      6.58             (s, 2H)                                                      ______________________________________                                    

Infrared spectrum:

1630 cm⁻¹ (C═O)

Mass Spectral analysis (m/e):

107, 150 (m), 135, 39, 41, 91.

The NMR spectrum is set forth in FIG. 1. The Infrared spectrum is setforth in FIG. 2.

The second (about 80% of the product mixture) is found to be4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one (compound B) andexhibits the following spectral properties:

    ______________________________________                                        NMR (δ) ppm                                                                              Interpretation                                               ______________________________________                                        1.16             (s, 3H)                                                      1.28             (s, 3H)                                                      1.44             (s, 3H)                                                      1.81             (d, 3H)                                                      2.02             (s, 2H)                                                      6.41             (d, 1H)                                                      ______________________________________                                    

Infrared spectrum:

1630 cm⁻¹ (C═O)

Mass Spectral analysis (m/e):

112, 69, 43, 39, 41, 84

The NMR spectrum is set forth in FIG. 3. The Infrared spectrum is setforth in FIG. 4.

The reaction mixture is poured into 500 of water and the organics areextracted with four 100 ml portions of ether. The ether is removed bymeans of a rotary evaporator and the two products are separated by meansof a careful distillation. Compound A is obtained first and has a b.p.of 60° C at 1.5 mm. Compound B distills second with a b.p. of 100° C at1.5 mm.

EXAMPLE III PREPARATION OF2,7,9,9-TETRAMETHYL-1,4-DIOXASPIRO[4,5]DEC-6-EN-8-ONE ##STR22##

To a 2 liter flask fitted with a reflux condenser, a water separator anda stirrer is charged 265 g of 2,6,6-trimethylcyclohex-2-en-1,4-dione(prepared by the method described in Helv.Chim.Acta. 39, 2041 (1956)),266 g of propylene glycol, 500 ml of benzene and 1 g ofp-toluenesulfonic acid. The reactants are stirred and refluxed until noadditional water is collected in the water separator. The product iswashed with water to a pH of 6 and the solvent is stripped off. Theresidue is vacuum distilled through a 9 inch Goodloe column to yield 257g of product, b.p. 92° at 1 mm Hg (80% yield).

EXAMPLE IV PREPARATION OF4-BUTYL-4-HYDROXY-3,5,5-TRIMETHYL-2-CYCLOHEXEN-1-ONE ##STR23##

A solution of 20 g of2,7,9,9-tetramethyl-1,4-dioxaspiro-[4,5]dec-6-en-8-one (prepared by themethod of Example III) in hexane is stirred while a solution of n-butyllithium in hexane is added dropwise. When no additional exothermoccurred the addition is stopped and the mixture is stirred for about 15minutes. Water is added with stirring to hydrolyze the lithium salt. Theorganic layer is separated and the hexane is allowed to evaporate,leaving oily crystals which are recrystallized from cyclohexane yielding10 g of 4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one, m.p.90°-93° C. The compound exhibits the following spectral characteristics:

    ______________________________________                                        NMR (δ) ppm                                                                              Interpretation                                               0.87             (t, 3H)                                                      1.02             (s, 3H)                                                      1.05             (s, 3H)                                                      1.05-2.1         (complex signals, 4H)                                        1.98             (s, 3H)                                                      2.35             (q, 4H)                                                      ______________________________________                                    

Infrared analysis:

1640 cm⁻¹ (C═O)

Mass Spectral analysis (m/e):

43, 41, 29, 39, 27, 28, 111, 154, 210 (m).

The NMR spectrum is set forth in FIG. 5. The Infrared spectrum is setforth in FIG. 6.

EXAMPLE V GERANIUM PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                        Geraniol Coeur         100.0                                                  Citronellol Coeur      130.0                                                  Linalool               5.0                                                    Citronellyl Formate    25.0                                                   Geranyl Acetate        10.0                                                   Benzyl 2.0                                                                    Guaicwood 10.0                                                                4-Hydroxy-2,4,6,6-tetra-                                                      methylcyclohex-2-en-1-one,                                                    produced according to                                                         Example II             30.0                                                   ______________________________________                                    

The 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one imparts the green,minty, herbaceous tone of geranium to this synthetic geraniumformulation.

EXAMPLE VI PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram of the perfumecomposition of Example V until a substantially homogeneous compositionis obtained. The perfumed soap composition exhibits a green, minty,herbaceous note so essential to geranium.

EXAMPLE VII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (Lysine salt ofn-dodecylbenzenesulfonic acid, as more specifically described in U.S.Pat. No. 3,948,818, issued on Apr. 6, 1976) is mixed with 0.15 grams ofthe perfume composition of Example V until a substantially homogeneouscomposition is prepared. This composition exhibits a green, minty,herbaceous note so essential to geranium.

EXAMPLE VIII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 grams oftalcum powder with 2 grams of the composition of Example V. It has agreen, minty, herbaceous note so essential to geranium.

EXAMPLE IX PERFUMED LIQUID DETERGENT

Concentrated liquid detergent (Lysine salt of n-dodecylbenzenesulfonicacid, as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976) with a geranium character is obtained containing 1.0%,1.5% and 2.0% of the composition of Example V. It is prepared by addingand homogeneously mixing the appropriate quantity of the composition ofExample V in the liquid detergent. The detergents all possess a geraniumaroma with green, minty and herbaceous notes, the intensity increasingwith greater concentrations of the composition of Example V.

EXAMPLE X COLOGNE

The composition of Example V is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). A distinctand definite geranium fragrance containing green, minty and herbaceousnotes essential to geranium is imparted to the cologne and to thehandkerchief perfume.

EXAMPLE XI PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-oneprepared according to Example II. It has an excellent green, minty andherbaceous aroma.

EXAMPLE XII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzenesulfonicacid, as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976) with a green, minty and herbaceous aroma are preparedcontaining 0.10%, 0.15% and 0.20% of4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one prepared according toExample II. They are prepared by adding and homogeneously mixing theappropriate quantity of 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-onein the liquid detergent. The detergents all possess a green, minty andherbaceous aroma, the intensity increasing with greater concentrationsof 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one.

EXAMPLE XIII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

4-Hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one prepared according tothe process of Example II is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). A distinctand definite green, minty and herbaceous aroma is imparted to thecologne and to the handkerchief perfume.

EXAMPLE XIV PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram of4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one of Example II until asubstantially homogeneous composition is obtained. The perfumed soapcomposition manifests an excellent green, minty and herbaceous aroma.

EXAMPLE XV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder (Lysine salt ofn-dodecylbenzenesulfonic acid, as more specifically described in U.S.Pat. No. 3,948,818, issued on Apr. 6, 1976) is mixed with 0.15 g of the4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one of Example II until asubstantially homogeneous composition is obtained. This composition hasan excellent green, minty and herbaceous aroma.

EXAMPLE XVI

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Bright            40.1                                                        Burley            24.9                                                        Maryland           1.1                                                        Turkish           11.6                                                        Stem (flue cured) 14.2                                                        Glycerine          2.8                                                        Water              5.3                                                        ______________________________________                                    

The above tobacco is used in producing cigarettes and the followingformulation is compounded and incorporated into each of thesecigarettes.

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Ethyl Butyrate     .05                                                        Ethyl valerate    .05                                                         Maltol            2.00                                                        Cocoa Extract     26.00                                                       Coffee Extract    10.00                                                       Ethyl Alcohol     20.00                                                       Water             41.90                                                       ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with the4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one produced according toExample II at 200 ppm per cigarette. Another third of these modelcigarettes are treated in the filter with the4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one at the rate of 2 × 10⁻⁵gm. and 3 × 10⁻⁵ gm. When evaluated by paired comparison, the cigarettestreated both in the tobacco and in the filter with the4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one are found, in smokeflavor, to be more aromatic, sweeter, cooling (sensation in the mouth)and containing sweet tobacco-like, floral and green nuances.

EXAMPLE XVII

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Bright            40.1                                                        Burley            24.9                                                        Maryland           1.1                                                        Turkish           11.6                                                        Stem (flue cured) 14.2                                                        Glycerine          2.8                                                        Water              5.3                                                        ______________________________________                                    

The above tobacco is used in producing cigarettes and the followingformulation is compounded and incorporated into each of thesecigarettes:

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Ethyl Butyrate     .05                                                        Ethyl valerate    .05                                                         Maltol            2.00                                                        Cocoa Extract     26.00                                                       Coffee Extract    10.00                                                       Ethyl Alcohol     20.00                                                       Water             41.90                                                       ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with the4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one produced accordingto Example IV at 200 ppm per cigarette. Another third of these modelcigarettes are treated in the filter with the4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one at the rate of 2 ×10⁻⁵ gm. and 3 × 10⁻⁵ gm. When evaluated by paired comparison thecigarettes treated both in the tobacco and in the filter with the4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one are found in smokeflavor to have sweet hay notes, tobacco-like notes and Virginia fluecured-like notes; and are also found to be more aromatic and Virginiatobacco-like.

EXAMPLE XVIII RASPBERRY FLAVOR FORMULATION

The following formulation is prepared:

    ______________________________________                                        Ingredient        Parts by Weight                                             ______________________________________                                        Raspberry ketone  4                                                           (oxyphenylon)                                                                 Vanillin          1                                                           Maltol            2                                                           Alpha-ionone      0.5                                                         Isobutylacetate   20                                                          Ethylbutyrate     5.5                                                         Dimethyl sulfide  1                                                           Acetic acid       30                                                          Acetaldehyde      16                                                          Propylene glycol  920                                                         ______________________________________                                    

When added at the rate of 1% to the above formulation the4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one adds a more naturalcharacter thereto. A 5-member bench panel unanimously agrees that theformulation containing 1% of4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one is moreraspberry-kernel like; more piney; has a wild raspberry or herbaceoustaste and has a natural berry character. The flavor formulationcontaining the 1% of 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one isunanimously preferred over the flavor formulation not containing any4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one. The flavorformulations are compared side-by-side at the rate of 40 ppm in water.

EXAMPLE XIX

The following mixture is prepared:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Natural Raspberry                                                             Concentrate Juice      2 1/2%                                                 Water                  85%                                                    Sugar syrup,                                                                  (37.5° Baume)   12 1/2%                                                ______________________________________                                    

The wild raspberry, herbaceous and seedy, raspberry kernel notes of thisraspberry juice is imparted in increased strength by addition of4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one at the rate of from 20parts per million up to 50 parts per million.

EXAMPLE XX

To the raspberry formulation of Example XVIII,4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one at the rate of 0.2% isadded. This material is then called the "test composition". Theraspberry formulation without4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one is called the "controlcomposition".

The test and control compositions are added to the food productsdescribed hereinafter in the proportions shown for 10 kilograms ofmaterial to be flavored:

    ______________________________________                                        Pudding         5-10 grams (0.15-.1%)                                         Cooked sugar    15-20 grams (.15-2%)                                          ______________________________________                                    

Cooked sugar -- 100 ml of sugar syrup (prepared by dissolving 1 kilogramof sucrose in 600 ml of water) and 20 grams of glucose are mixedtogether and slowly heated to 145° C. The flavor is added and the massallowed to cool and harden.

Pudding -- To 500 ml of warmed milk are added with stirring a mixture of60 grams sucrose and 3 grams of pectin. The mixture is boiled for a fewseconds and the flavor is added. The mixture was allowed to cool.

The finished foodstuff samples are tested by a panel of trained personswho express their views about the flavor of the samples. All members ofthe panel prefer the test samples having a more distinguished wildraspberry aroma with taste of the wild raspberries and its herbaceousand kernel notes.

What is claimed is:
 1. A process for augmenting or enhancing theorganoleptic properties of a foodstuff by adding to said foodstuff from0.5 parts per million up to about 100 parts per million based on thetotal composition of 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one.2. A flavor modifying composition comprising about 0.1% up to about 15%by weight based on the total weight of the composition of4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one and as a flavoradjuvant a compound selected from the group consisting ofp-hydroxybenzyl acetone, maltol, benzyl acetate, methyl cinnamate,geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate,alpha-ionone, gamma undecalactone, ethyl pelargonate, isoamyl acetate,acetaldehyde, dimethyl sulfide, isobutyl acetate, acetic acid, ethylbutyrate, diacetyl, anethole, cis-3-hexenol-1, naphthyl ethyl ether,ethyl acetate, isoamyl butyrate, 2-methyl-2-pentenoic acid,2-(4-hydroxy-4-methylpentyl)-norbornadiene,4-allyl-1,2,6-trimethoxybenzene, cassia oil, eugenol, caryophyllene,guiacol, cinnamaldehyde, 5-methylfurfural, cuminaldehyde, cinnamylformate, methyl cinnamate, furfural, 2,3-dimethylpyrazine,2-ethyl-3-methylpyrazine, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, 3-phenyl-4-pentenal diethyl acetal,1-crotonyl-2,2,6-trimethylcyclohex-1-ene,1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene,2,2,6-trimethylcyclohex-1-ene carboxaldehyde and4-propenyl-1,2,6-trimethoxybenzene.